Process for the preparation of copoly(arylene sulfide)

ABSTRACT

A process for preparing a copoly(arylene sulfide) corresponding to the structure 
     
         [(--A--S--).sub.1-x (--A--S--S--).sub.x ].sub.n 
    
     wherein x is in the range of 0.5 to 0.001 by reacting a mixture of a diiodoaromatic compound and elemental sulfur in the absence of a basic material and in the presence of a catalytic amount of an organic amine-containing compound.

This application is a continuation-in-part of Ser. No. 220,404, filedJune 28, 1988, now abandoned.

The invention relates to a process for the preparation of acopoly(arylene sulfide) by heating a diiodoaromatic compound andelemental sulphur in the absence of a basic material and in the presenceof a catalytic amount of an organic amine-containing compound.

Poly(acrylane sulfide) (PAS) resins are thermoplastic polymericmaterials with good thermal stability, unusual insolubility, resistanceto chemical environments and inherent flame resistance. PAS resinsadditionally have good electrical insulative properties which make themideal for electrical and electronic applications. Their excellentresistance to chemical degradation makes them ideal for use in chemicalenvironments which involve organic solvents and strong mineral acids,such as coatings for pipes, tanks, pumps and other equipment.

Poly(phenylene sulfide) (PPS) is a commercial product which is generallyproduced by reacting p-dichloro-benzene with sodium sulfide in a polarorganic solent to produce PPS and the by-product sodium chloride. Thisprocess is known as the Macallum polymerization procedure and the basicprocess is disclosed in U.S. Pat. No. 2,513,188 and U.S. Pat. No.2,538,941. An improvement on the Macallum polymerization procedureinvolves adding N-haloamides as catalysts in the procedure (U.S. Pat.No. 3,285,882). The Macallum polymerization utilizes only chloroaromaticcompounds.

The PPS which is formed in the Macallum process has only a modestmolecular weight on the order of 10,000-40,000 and has relatively lowmelt viscosity. Higher molecular weights can be obtained by heating thePPS in the presence of oxygen. During heating, the molecular weight ofthe PPS increases due to a variety of chemical reactions includingoxidation, crosslinking and chain extension. These curing reactionsresult in polymers which have inherent brittleness and reduced drawingcapability while only achieving modest increases in molecular weight.Additionally, PPB which is produced by polymerization in the presence ofsulfide and/or hydrosulfide salts, such as sodium sulfide and sodiumhydrosulfide, has a residual content of inorganic salt present in thepolymer. These residual salts are, for example, sodium chloride andsodium sulfide resulting from the combination of the sodium cation withchlorine or sulfide from the starting materials. The presence of theseresidual salts in the polymer increases the corrosive nature of thepolymer and can cause a deterioration in the drawing or spinningcharacteristics of the polymer. Residual salts can also result inbreakages in the spun fibers and additionally contribute to plugging andclogging of the spinneret holes.

An additional problem with poly(acrylene sulfide) produced by theMacallum process is the effect of residual salts on the electricalproperties. The presence of residual salts results in polymers withincreased moisture adsorption and electrical activity, which aredetrimental to applications requiring highly insulating characteristics.Although extensive extraction reduces the salt content of PPS producedby the Macallum process, complete removal of these salts is commerciallyinfeasible.

An additional problem with PPB produced by the Macallum process is thehigh rate of crystallization of these polymers. Although someapplications do require high rates of crystallization, many applicationsrequire much slower rates of crystallization. These polymers contain nosubstantial quantities of disulfide units.

U.S. Pat. No. 4,645,826 discloses a process of preparing "ultra-highmolecular weight" linear PAS by first preparing a prepolymer with a meltviscosity between 5-3,000 poise and then performing a liquid-liquidtwo-phase polymerization. Only dichloroaromatic compounds are disclosedand the prepolymer is formed using a conventional alkaline metalsulfide. The "ultra-high molecular weight" polymers have meltviscosities of only tens of thousands of poise. The prepolymer is formedby a standard Mascallum polymerization in the presence of an alkalimetal sulfide. Accordingly, the polymers produced will suffer from theproblem associated with residual salt content noted above. Thesepolymers are also through to contain no substantial quantities disulfideunits.

U.S. Pat. No. 4,645,825 also discloses poly(arylene sulfide) producedusing dichloroaromatic or dibromoaromatic compounds and polymerizing inthe presence of conventional alkaline metal sulfides or hydrosulfides.Although polymers with relatively high molecular weights and meltviscosities can be produced by this process, the presence of residualinorganic salts in the polymer results in inferior corrosioncharacteristics as well as poor spinning and drawing capability. Thesepolymers are also thought to have no substantial quantities of disulfideunits.

Copending U.S. application Ser. No. 211,180 discloses preparation ofco(polyarylene sulfides) by heating a diiodoraromatic compound in thepresence of elemental sulfur.

This process can be used to prepare poly(arylene sulfide) which do notcontain substantial quantities of alkali metals and has an adjustablerate of crystallization. The copolymers prepared using the process ofthis invention do not contain substantial quantity of alkali metalssimply because no alkali metal is used in the process used to preparethe polymer. Although Applicants do not wish to be limited to anyparticular theory, it is believed that the variable rate ofcrystallization of the copolymer prepared using the process is due tothe presence of small amounts of (--A--S--) or disulfide units in thepolymer chain. Thus, the prepolymers prepared by this process can beconsidered to be copolymers. The presence of these disulfide units inthe copolymer do not materially affect other important properties of thepolymer, such as glass transition temperature, solvent resistance,thermal stability, and oxidative stability.

The vast majority of units in the copolymer prepared by the process ofthis invention are the (--A--S--) unit and the number of (--A--S--S--)or disulfied units are small compared to the number of (--A--S--) units.Generally, the number of (--A--S--S--) units is in the range of 0.5 to0.001, based on the combined number of both (--A--S--) and (--A--S--S--)units. Thus, the copolymer prepared by the process of the invention canbe represented as

    (--A--S--).sub.1-x (--A--S--S--).sub.x

where x is in the range of 0.5 to 0.001. The sequence of (--A--S--) and(--A--S--S--) unit is thought to be random throughout the molecularchain. When x is in the range of 0.5 to 0.2 the polymers obtained when Ais p-phenylene are amorphous and can be crystallized only withdifficulty. When x is in the range of 0.2 to 0.1 the polymers obtainedcan be thermally crystallized and have crystalline melting points of230-260 degree C. When x is in the range of 0.1 to 0.5 the polymersobtained have moderate crystallization rates and the crystallizedpolymers can be annealed to high crystalline melting points (280°-290°C.) and show Tch (temperature of crystallization on heating) and Tcc(temperature of crystallization on cooling) at increasingly lower andhigher temperatures, respectively, indicative of increasing rates ofcrystallization. When x is in the range of 0.05 to 0.001 thecrystallization rate increases rapidly with decreasing x.

The following table more clearly shows the effect of disulfide units onthe crystallization rate of poly(phenylene sulfide):

    ______________________________________                                        X       Tg      Tcc    Tch    Tm   T 1/2 (130° C.)                     ______________________________________                                        0.25    88      --     --     238                                             0.14    90      --     --     251                                             0.12    94      --     --     255  132 Seconds                                0.10    92      168    --     243                                             0.064   94      142    231    280                                             0.055   95      140    226    278                                             0.049   95      126    240    280                                             0.000   91      126    242    278  12 Seconds                                 ______________________________________                                    

The size of the polymer chain can conveniently be expressed as the totalnumber of each kind of unit in the chain. Therefore, the copoly(arylenesulfide) prepared by the process of this invention can be morespecifically expressed as corresponding to the structure

    [(--A--S--).sub.1-x (--A--S--S--).sub.x ].sub.n

wherein n, the degree of polymerization, is at least 200 and ispreferably in the range of 500 to 5,000 as determined by melt viscositymeasurement at 300° C. The degree of polymerization when A isp-phenylene can be calculated using the relationship log(n)=1.473+0.2873×log (melt viscosity) where melt viscosity is measuredin poise.

In the process used to prepare the co(polyarylene sulfide) of thepresent invention a diiodoarylene compound corresponding to thestructure

    I--A--I

where A is a divalent arylene radical is reacted with elemental sulfurto produce a substantially linear copoly(arylene sulfide) having both(--A--S--) units and (--A--S--S--) units in the presence of an effectiveamount of catalyst.

Diidoaromatic compounds which can be utilized in the present processinclude unsubstituted or substituted aromatics which have two iodinesubstituents. Suitable diiodoaromatic compounds include hydrocarbonaromatics, nitrogen-containing aromatic, sulfur-containing aromatics andoxygen-containing aromatics. Typical hydrocarbon aromatics includebensene and biphenyl, and condensed ring aromatics such as naphthaleneand anthracene. Typical sulfur-containing aromatics include, forexample, thiophene and benzothiophene. Typical nitrogen-containingaromatics include pyridine and quinoline. Suitable oxygen-containingaromatics are, for example, furan, dibenzofuran, etc. Substituteddiisodoaromatic compounds suitable for use with the present inventioninclude aromatic sulfones, diarylethers, diarylcarbonyls, diarylsulfidesand the like.

The aromatic structure materials may be substituted by one or more alkylgroups, preferably alkyl groups having from 1-6 carbon atoms. Speciallypreferred alkyl groups are methyl, ethyl, propyl and butyl groups. Thereis no limitation on the spatial arrangement of the substituents, forexample, the substituents may be on a carbon adjacent to an iodinebearing carbon or may be on a carbon atom further removed from theiodine bearing carbon.

Additional substituents on the aromatic compounds may include phenyl,halogen, hydroxy, nitro, amino, C₁₋₆ alkoxy, and carboxylate andcarboxylic acid substituents, as well as aryl sulfones and aryl ketones.

Preferred diiodoaromatic compounds are the diiodobenzenes,diiodonaphthalenes, diiodobiphenyls, diiodopiphenyl ethers anddiiodotoluenes which may be unsubstituted or substituted with any of thesubstituents noted above.

Specific diiodoaromatic compounds suitable for the present inventioninclude p-diisodobenzene, m-diiodobenzene, p,p'-diiodobiphenyl,m,p'-diiodobiphenyl, p,p'-diiododiphenyl sulfone, p,p'-diiodopiphenylether, 2,6-diiodonaphthalene, and p,p'-diiodobenzophenone.p-Diiodobenzene, p,p'-diiodobiphenyl, and p,p'-diiododiphenyl ether aremost preferred.

The diiodoaromatic starting materials of the present invention may beprepared by any suitable process. For example, the diiodoaromaticcompounds may be prepared by standard liquid or gas phase iodinationreactions. Although the diiodoraromatic compounds may be prepared by anysuch process, the preferred method of preparing the diiodoaromaticstarting materials is that disclosed in copending application Ser. Nos.912,806, filed Sept. 9, 1986, U.S. Pat. No. 4,746,758; 026,896, filedMar. 25, 1987; 029,959, filed Mar. 25, 1987, U.S. Pat. No. 4,795,737;and 029,898, filed Mar. 25, 1987, now U.S. Pat. No. 4,792,642.Alternatively, the diiodoaromatic compounds may be produced by atransiodination process such as that disclosed in copending applicationSer. Nos. 029,899, filed Mar. 25, 1987, U.S. Pat. No. 4,792,641;029,956, filed Mar. 25, 1987, U.S. P at. No. 4,806,698; and 029,949,filed Mar. 25, 1987, U.S. Pat. No. 4,806,697. The disclosures of thesecopending applications are incorporated herein by reference for a morecomplete description of these preferred processes.

Sulfur is reacted as elemental sulfur and may consist of any of thestandard forms which are possible for elemental sulfur. That is, thesulfur may be present in any of its allotropic modifications such asorthorhombic cyclooctasulfur (S₈) or any other cyclic elemental sulfursuch as any of the cyclosulfur species having 6-12 sulfur atoms.Additionally, any crystalline forms of sulfur may be used in the presentreaction. Surprisingly, impurities in the elemental sulfur do not appearto affect the efficiency or selectivity of the present polymerizationreaction. The sulfur preferably has a purity of about 98%-100%, althoughsulfur having a lower degree of purity may be used. This lack ofsensitivity to the presence of impurities in the sulfur is advantageousto the present process when used as a commercial process since highlypurified sulfur is not required and the associated expense is notincurred.

An important aspect of this invention is the use of a catalyst toenhance the rate of reaction. The catalysts disclosed in this inventioncan be broadly thought of as organic amine-containing compound which canbe primary, secondary, tertiary or quaternary amines. The substituentscan be alkyl containing 1 to 20, preferrably 1 to 10, carbon atoms oraromatic, containing 6 to 20 carbon atoms. The alkyl and aromaticsubstituents may be further substituted with halogen, hydroxy, amino,carboxy, or cyano substituents. Examples of suitable catalysts includeaniline, N-dimethylaniline, pyridine, quinoline, 4-iodoaniline, tributylamine, trioctylamine, diphenyl amine, and carbazole. Quinoline,trioctylamine, and aniline are preferred with quinoline being mostpreferred.

The amount of catalyst can be any quantity which results in an enhancedrate of reaction. Generally at least 0.001 mole percent, based on thetotal moles of diiodoaromatic compound is used. Preferably the catalystis in the range of 0.01 to 5.0, preferably 0.05 to 0.5 mole percentbased on the total moles of diiodoaromatic compound.

In the process used to prepare the co(polyarylene sulfide) of thisinvention sulfur reacts with a diiodoaromatic compound, eliminatingelemental iodine and forming the PAS as shown below.

    nArI.sub.2 +nS→(--Ar----).sub.n +nI.sub.2

The formation of polymer is not sensitive to the relative stoichiometryof the diidoaromatic compound and sulfur. Accordingly, an excess ofsulfur or an excess of diiodoaromatic compound may be used in thepolymerization process. When excess sulfur is used, some disulfidelinkages are observed in the polymer. Decreasing amounts of sulfurresult in decreasing levels of disulfide linkages in the final polymer.When the diisodoaromatic compound is present in excess, polymerizationto high polymer can still occur, if the excess diiodoaromatic compoundis removed during final polymerization.

The polymerization reaction is preferably carried out in the absence ofsolvent by merely heating and reacting the sulfur and diiodoaromaticcompound. Under these conditions, the diidoaromatic compound itself actsas a solvent for the sulfur which is melted thereby forming asubstantially homogeneous solution enabling a facile and completereaction.

In another embodiment, the diiodoaromatic compound can be dissolved inan organic solvent which is inert to the reaction conditions, i.e.,which is inert to reaction with iodine and sulfur. High boiling inertaromatic solvents are preferred such as, for example, aromatichydrocarbons, diarylsulfides, diarylethers and diarylsulfones. It ispreferable to use a solvent which corresponds to the diiodoaromaticcompound which is being polymerized. Thus, for example, in thepolymerization of diiodobenzene with sulfur, one might use benzene,toluene or naphthalene as a solvent.

It is also possible to perform the polymerization reaction of thepresent invention by solid state polymerization. Solid statepolymerization enables very high molecular weights and melt viscositiesto be achieved. After an initial melt polymerization (or alternativelysolution polymerization) has been performed, the product is cooled to asolid state. Further heating and polymerization in the solid state undervacuum or inert gas flow dramatically increases the molecular weightallowing weight average molecular weights in excess of 100,000 to beachieved. It is significant to note that substantially no cross-linkingoccurs during the solid state or melt polymerization processes. The veryhigh molecular weight copolymers which are produced after the solidstate polymerization are still substantially linear and have excellentfilm and fiber forming properties.

During the polymerization reaction between the diiodoaromatic compoundand sulfur elemental iodine is produced and evolves from the reactionmelt, solution, or solid. Removal of the elemental iodine provides adriving force for completion of the polymerization reaction. The iodinemay be removed by passing a stream of air or an inert gas such asnitrogen or argon over or through the reaction mass at atmospheric orsuperatmospheric pressure or alternatively by applyong a vacuum to thereaction apparatus. The elemental iodine may be collected and used as acommercial product or as a reactant for further chemical processes. Thepresent reaction, therefore, does not result in wasted reaction productsand production of hazardous waste streams since both the PAS andelemental iodine are useful commercial chemical products.

The polymerization reaction is generally conducted at a temperatureabove about 175° C. Although the reaction may be conducted attemperatures below 175° C., the polymerization reaction is much slower.There is no particular upper temperature limit on the polymerizationreaction, which may be conducted at any temperature below thedecomposition temperature of the diidodoaromatic compound. For mostpolymerization reactions, temperatures in the range of about 175°-400°C. will be suitable, although for particular diidoaromatic compoundstemperatures in excess of 400° C. may be used. Particularly preferredtemperature ranges are from about 180°-350° C.

The reaction is generally conducted for a period of at least one-halfhour and is continued for up to about 10 hours or longer, and reactiontimes approaching infinity are theoretically possible. The exactreaction time will depend on the diiodoaromatic compound, theengineering requirements of the process, and the specific molecularweight, viscosity and physical properties of the desired product.

The polymerization reaction may be carried out in a batch reactionvessel or may be carried out as a semi-continuous or continuous process.Agitation of the reaction mixture is optional, however agitation orstirring assists in the production and yield of the polymeric product.Agitation of the reaction mixture may be accomplished by any knownmethod, such as mechanical stirring or by passing a stream of inert gasthrough the reaction mixture.

In a preferred embodiment, the polymerization reaction is conducted on acontinuous basis with the diiodoaromatic compound and sulfur beingcombined in a continuous staged reactor to form a reaction melt. Aninert gas such as nitrogen or argon is passed through the melt,preferably in a countercurrent direction, thereby accomplishingagitation and mixing of the reaction melt and at the same time removingthe elemental iodine which is evolved and sweeping it out of thereactor. Alternatively, a vacuum may be applied to the reactor to removethe elemental iodine as it is generated. It should be noted that thereaction proceeds equally well under batch conditions and combinationsof batch and continuous processes are considered to be well within thescope of the present invention.

The copolymer produced by the process of this invention is useful forpreparation of various shaped articles such as pellets, fibers andmolded articles. The polymer can be prepared into these shaped articlesby conventional processes, such as injection molding and melt spinning.

Since there are no alkali metal-containing materials in the reaction,there are no substantial quantities of alkali metal in the polymermatrix. Typically there is less than 100 weight parts per million alkalimetal, preferably less than 10 weight parts per million, based on theweight of the copoly(arylene sulfide). The absence of substantialquantities of alkali metal greatly enhance the capability of the polymerto be melt processed, particularly melt spun into fibers.

The copoly(arylene sulfide) and particularly the copoly(phenylenesulfide) produced by the process of this invention have an adjustablerate of crystallization, due to the presence of the disulfide linkages.Since the concentration of disulfide linkages can be varied over a widerange, the rate of crystallization can be readily adjusted to suit thetechnological application without unduely sacrificing other desirablecharacteristics of the polymer. In addition, the rate of crystallizationcan be further enhanced by the addition of conventional nucleating aidssuch as talc, terephthalic acid, silica or the like for thoseapplications where extremely fast rates are desired.

An important aspect of this invention is reacting the diiodoaromaticcompound and elemental sulphur in the absence of a substantial amount ofbasic material. Examples of basic materials which are not present in ourreaction include dithionates, lithium hydroxide, sodium hydroxide,potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesiumhydroxide, calcium hydroxide, strontium hydroxide, sodium hydroxide,sodium carbonate, potassium carbonate and the like.

Other features of the invention will become apparent in the course ofthe following descriptions of exemplary embodiments which are given forillustration of the invention and are not intended to be limitingthereof.

EXAMPLES

In the following examples, the catalytic activity of variousamine-containing compounds was examined by measuring the rate of iodineevolution from mixtures of 10.0 grams of p-diiodobenzene, 1.00 gramssulfur, and the indicated amount of the indicated amine-containingcompound held at 235° C. at atmospheric pressure in a thermostatted heatblock. No basic materials were present in the reaction medium. Theresults are tabulated below:

    ______________________________________                                                  Organic                                                             Example   Amine-Containing                                                                             Mole     Rate                                        No.       Compound       Percent.sup.1                                                                          Constant.sup.2                              ______________________________________                                        1         --             --       0.0038                                      2         4-iodoaniline  0.10     0.0110                                      3         trioctylamine  0.10     0.0118                                      4         quinoline      0.10     0.0172                                      5         diphenylamine  0.10     0.0057                                      6         quinoline      0.01     0.0134                                      7         --             --       0.0034                                      ______________________________________                                         .sup.1 Based on the moles of pidiiodobenzene                                  .sup.2 Lmol.sup.-1 min.sup.-1 -                                          

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

We claim:
 1. A process for producing elemental iodine and acopoly(arylene sulfide) corresponding to the structure:

    [(--A--S--).sub.1-x (--A--S--S--).sub.x ].sub.n

wherein A is a divalent substituted or unsubstituted aromatic racial, xis in the range of 0.5 to 0.001 and n is at least 200, comprising(1)reacting at a temperature above about 175° C. a mixture consistingessentially of a diiodoaromatic compound and elemental sulfur and anorganic amine-containing compound to produce the elemental iodine andthe copoly(arylene sulfide), and (2) recovering the elemental iodine. 2.The process of claim 1 wherein the diiodoaromatic compound is selectedfrom the group consisting of diiodohydrocarbon aromatics,sulfur-containing diiodoaromatics, nitrogen-containing diiodoaromaticsand oxygen-containing diiodoaromatics.
 3. The process of claim 2 whereinsaid diiodoaromatic compound is substituted with one or more alkylgroups having 1-6 carbon atoms.
 4. The process of claim 1 wherein saiddiiodoaromatic compound is substituted with a member selected from thegroup consisting of phenyl, halogen, hydroxy, nitro, amino, C₁₋₆ alkoxy,carboxylate, carboxylate acid, aryl sulfone and aryl ketone groups. 5.The process of claim 1 wherein said diiodoaromatic compound is selectedfrom the group consisting of diiodobenzenes, diiodonaphthalenes,diiodobiphenyls and diiodotoluenes.
 6. The process of claim 1 whereinsaid diiodoaromatic compound is p-diiodobenzene, m-diodobenzene,p,p'-diiodobiphenyl, p,p'-diiodophenyl ether, or 2,6-diiodonaphthalene.7. The process of claim 1 wherein said reacting step is conducted at atemperature between about 175°-400° C.
 8. The process of claim 7 whereinsaid reacting step is conducted at a temperature between about 180°-350°C.
 9. The process of claim 1 wherein said reacting step is conducted inthe presence of an inert solvent.
 10. The process of claim 1 whereinsaid reacting step is a solid state polymerization.
 11. The process ofclaim 1 wherein said reacting step is conducted as a continuous processand wherein an inert gas is passed through said reaction mixture. 12.The process of claim 1 wherein the amount of organic amide-containingcompound in the range of 0.01 to 5.0 mole percent.
 13. The process ofclaim 12 wherein the amount of organic amide-containing compound is inthe range of 0.05 to 0.5 mole percent.
 14. The process of claim 1wherein the organic amine compound is arylamine.
 15. A process forproducing elemental iodine and a copoly(phenylene sulfide) correspondingto the structure

    [(--A--S--).sub.1-x (--A--S--S--).sub.x ].sub.n

where A is a divalent unsubstituted phenylene radical, x is in the rangeof 0.5 to 0.001, and n is at least 400, comprising(1) reacting a mixtureof consisting essentially of diiodobenzene and elemental sulfur and anorganic amine-containing compound at a temperature in the range of 180°to 350° C., where the organic amine-containing compounds is in the rangeof 0.001 to 1.0 mole percent based on the mole of p-diiodobenzene. (2)recovering the elemental iodide.